Novel petroleum resin process



mr., 1956 B. R. TEGGE ET AL if? NOVEL PETROLEUM RESIN PROCESS Filed July2, 1953 HIGH PRESSURE STEAM l@ HYDWLVEE @I l i3 w SEMLER D SOAKER i NUL@mmmj d WAVE ALL@ D swf 2 wwss l www@ @mmm WAT@ m@nu` wAswN monomericcyclopentadienes.

United States Patent O NOVEL PETROLEUM RESIN PROCESS Bruce R. Tegge,Chatham, and Fred W. Balles, Westfield,

N. J., assgnors to Esso Research and Engineering Company, a corporationof Delaware Application July 2, 1953, Serial No. 365,739

8 Claims. (Cl. 2ML-82) This invention relates to a novel process for thecontinuous production of petroleum hydrocarbon resins and, moreparticularly, to a process in which petroleum resins are made by aseries of steps wherein the continuous synthesis, purification, andrecovery of resins from steam cracked petroleum distillate fractions arecarried out under critical conditions.

Hydrocarbon resins can be produced from certain petroleum refinerystreams containing olelins and dioletins by methods of polymerizationusing Friedel-Crafts catalysts. The steam cracked streams have beenfound especially useful for this purpose.

There has now been discovered an improved process for the production ofpetroleum resins by the AlCla catalyzed polymerization of steam-crackeddistillates, including high temperature liquid phase hydrolysis of thereactor effluent, ammonia protection of the distillation equipment, andcaustic washing of the overhead gasoline fraction after resin recovery.

In general, heavier petroleum fractions such as heavy naphtha, kerosene,gas oil, and the like, are cracked at relatively low pressures and attemperatures of 550 to 900 C. in the presence of steam and forrelatively short contact times. The naphtha distillate streams obtainedby these steam cracking operations contain relatively large amounts ofdiolefns, olens, aromatics, and some parafns. Urdinarily the liquidproducts are recovered as two streams by partial condensation of crackedproducts at approximately atmospheric pressure. One stream along with C4and lighter hydrocarbons is taken overhead and, after successive stagesof fractionation to remove C1, C2, C3 and C4 hydrocarbons, remains as aresidual light distillate containing C5 through Ca hydrocarbons. Thesecond stream recovered as condensate represents largely C7 plushydrocarbons boiling up to about 280 C. This stream may contain minorquantities of C5 and Ca hydrocarbons.

Although the combined C5 plus streams may be eml ployed aspolymerization feed naphtha, it is usually desirable to first treat thefeed to convert cyclopentadiene monomers to their dimer and codimerforms. These monomers, if present in the feed to the extent of more thanabout 2% by weight, will give gel (insoluble polymer) during the startup period of the polymerization. However, it is not desirable tothermally soak the C5- 280 C. stream to effect cyclopentadienedimerization since this tends to selectively polymerize certain activeunsaturated compounds as styrenes and indenes boiling in the G-250 C.range. Preferably then, the light Cs-Ca distillate is heat treated alonefor 6-9 hours at 90- 140 C. to convert cyclopentadiene monomers todimers. The heat treated stream is then blended with the heavierdistillate or is distilled with steam or under vacuum to separate dimersas a bottoms product. The overhead from this distillation will containless than 2 weight percent i It may be further topped to about 38o C. torecover a dilute isoprene fraction. Bottoms from this topping operation,together with any ice untopped material which by-passes thisdistillation, represent a desirable polymerization feed stream. Thisstream and the heavier distillate may be polymerized alone or incombination with each other.

The overall process of the invention includes the following necessarysteps after obtaining the steam-cracked fraction: v

1. Polymerization of the reactive hydrocarbons with fluid aluminumchloride catalyst `in such a manner that the catalyst concentration inthe reactor circulatory system is maximized at the point that thisstream contacts fresh olefinic feed.

2. Treating the` reactor effluent with water at about 300 F. andsuperatmospheric pressure.

3. Stripping unreacted naphtha and liquid polymer from the resin in thepresence of ammonia.

4. Alkaline hydrolysis of the overhead from step 3 with soda ash orsodium hydroxide solution at about C.

5. Distillation of the treated hydrocarbon from step 4 to recover agasoline fraction overhead and liquid polymer as a bottoms fraction.

The steam-cracked feed distillates are streams or fractions thereofboiling in the range of 20 to 280 C. and are further characterized bythe approximate composition:

Weight percent Dioletins 10-35 Olens 40-70 Aromatics 20-45 Parafn andNaphthenes 0-20 The appropriate distillate feed is pumped to the reactorcirculating system where it is mixed with the AlCla containing catalystand subsequently circulated through a cooler and reactor. After partialsettling of hydrocarbon and catalyst sludge phases in the reactor, thematerial from the top of the reactor is passed to :a soaker or time tankwhere, if desired, some of the catalyst sludge is separated. Anyseparated catalyst sludge may be either recycled to the reactor orpurged from the polymerization system. y

Although either AlCla or AlBra may be used in preparing petroleum resinsby this process, cost considerations favor ,the use of the former. Borontriiiuoride is less desirable since it tends to give lower molecularweight products. However, the direct use of solid AlCla in the reactionzone has been found to be difficult to manipulate and handle especiallywhen it is used in small quantities under careful control, as in thepolymerization process. Dispersions, complexes or sludges of AlCla in ahydrocarbon carrying medium can be handled most conveniently andmeteredor measured most satisfactorily.

For example, the solid AlCla can be reacted with the naphtha, orsteam-cracked distillate stream, to give reaction products containingfrom 10 to 50 weight percent catalyst. Ordinarilyfabout l0 to 50 weightpercent of solid AlCl3 is added to the hydrocarbon. feed to prepare thecatalyst. During the addition of the solid material, it is necessary tocool the reaction mixture, with agitation, in order to complete thedissolution or complexing of the solid catalyst. The resulting catalyticmaterial is a dark colored fluid.

However, it is more advantageous to use reactor etlluent or treatedresin solution as the slurrying or complexing medium since less heat isevolved upon addition of AlCla. Furthermore, the presence of dissolvedresin improves the stability and suspendability of the catalystpreparation so that a uniform, pumpable catalyst is produced.

The catalyst preparation usually contains 10 to 50% AlCls by weight andis prepared by adding the proper quantity of solid AlCla to an agitatedand water cooled vessel containing the resin solution. TheAlClz-hydrocarbon mixture is agitated at temperatures controlled to 70C. or Ilower until a uniform composition is attained. This catalystlargely represents complexes of the AlCls type with components of theresin solution and is stabilized with respect to settling by thedissolved resin.

Optimum resin yields are obtained at polymerization temperatures rangingfrom to 60 C. Higher polymerization temperatures are to be avoided inthis system since these conditions result in increased yields of lowmolecular weight by-product polymers and products. It is especiallydesirable-to po'lymerize the steam-cracked distillates under reactionconditions wherein the ratio of catalyst to olefmic reactants ismaintained as high as possible. This is accomplished by proper design ofthe reactor circulating system so that the catalyst concentration at thefresh feed inlet point is maintained as high as possible. This isaccomplished by:

(l) Taking product resin solution olf from the top of the reactor andreturning the recirculated reactor mixture to the reactor at some pointbelow the product draw-off. This increases the effective catalystconcentration in the reactor by preferential settling of the more densecatalyst complex or sludge phase.-

(2) Increasing the reactor pumparound circulation rate.

Fresh feed is pumped into the reactor circulating system at a rate of0.6 to 6.0 volumes per volume of reactor system per hour and thecontents of the reactor are recirculated at a rate of 20 to 300,preferably 50 to 250, reactor volumes per hour. Catalyst preparation isadded to the system at a rate equivalent to 0.1 to 2.0% by weight A1Cl3on the fresh feed and the AlCls in the circulating system of the reactoris maintained at 0.2 to 10% by weight on the reactor contents dependingon the amount of AlCla fed to the system per unit weight of fresh feed.

Operating in the above manner, product solution from the top of thereactor passes at a rate of 0.6 to 6.0 reactor volumes per hour to asecond stage wherein the reaction is completed. Alfter allowing time forthe catalyst to build up in the reactor, the catalyst concentration inthe solution going to the second stage will be essentially the same asthat added to fresh feed. The residence time in the second stage is 10to 75 minutes and as noted earlier any catalyst complex or sludge can bepartially separated in this stage and returned to the reactor or carriedon to the subsequent finishing stages.

It is most desirable to effectively complete the polymerization reactionin a minimum number of stages and this is accomplished by the aboveprocess wherein the bulk of the reaction occurs in the rst stage.

After suflicient residence time in a reactor soaking tank or settler,the reactor eflluent is lthen pumped through an orifice mixer. Here itis contacted with water at about 10D-200 C. and superatmosphericpressure to remove dissolved and entrained AlCls sludge and complexesfrom the hydrocarbon phase. High temperatures are emp'loyed to minimizethe emulsion formation and enhance phase separation rates by hydrolyzingand dissolving as much of the A'lCla complexes as possible in theaqueous phase. Because of the acid conditions in this system, protectivelinings of steel tanks and HClresistant alloys are used as constructionmaterials. Pumps, heat exchangers and the like can be avoided by directinjection of high pressure steam to maintain the hydrolyzing temperatureat about 10U-200 C.

Resin recovery is accomplished by ashing theV high pressure hydrocarbonphase into a low pressure flash drum where 1-20 weight percent of theunreacted naphtha is taken overhead. In order to control corrosion inthis drum a small amount of ammonia is added. The ash drum bottoms,which contain the bulk of the unreacted hydrocarbons and low molecularweight poly- 4 mer oils and resin, are pumped to a vaporizer furnace andflashed into a stripping tower. A small amount of ammonia is also addedto the vaporizer feed to control corrosion. The total ammonia added tothe system need be only 0.005 to 0.5 weight percent on the total resinsolution, the amount depending on the per cent by weight of catalystemployed. About 75-90% of the ammonia is injected into the vaporizerfeed stream. Ammonium chloride vapor is taken overhead by propermaintenance of the temperature and pressure conditions in the strippingtower. The combined overhead vapors from the low temperature llash drumand the stripper tower are condensed in one and preferably two or morestep-down stages and sent to a separator where water, containingammonium chloride and ammonia hydroxide, is removed.

Some alkyl chlorides are invariably produced by interaction of HCl witholenic compounds and since such compounds have a deleterious effect ongasoline quality it is usually necessary that they be converted to lessharmful materials. This is accomplished by treating the hydrocarbonsolution at to 200 C. with 0.05 to 0.5 volumes of 2l0--wt. percent NaOHor NazCOs solution. At these temperatures the alkyl chlorides arehydrolyzed to harmless hydroxy compounds. No emulsion problems areencountered by this high temperature treatment whereas treating resinsolution in the same manner at lower temperature often produces verystable emulsions.

After separating the caustic solution phase by settling, the hydrocarbonphase is fractionated to recover a Css-220 C. overhead gasoline cut andliquid polymer bottoms. The latter may be blended with the strippedresin to control resin softening point. The stripped resin bottoms fromthe high temperature stripping Zone may be diluted with suitablenaphthas and solvents for viscosity control if desired.

The process as outlined accomplished several objectives, including thefollowing:

(l) It provides for an operation that can be carried out with a minimumamount of corrosion-resistant equipment.

(2) it provides for the removal of catalyst residues from thepolymerizate solution thereby giving a lightcolored, non-corrosive,low-ash petroleum resin product.

(3) It provides for the removal of catalyst complexes and residues andalkyl chlorides from the unreacted portion of the naphtha feed(raffinate). The product naphtha is therefore a suitable component forgasoline.

(4) It provides for a practical method for increasing resin yield andquality by maintaining the ratio of AlCls sludge to diolelin in thereaction zone at an increased level.

(5) It provides a practical method for removing the AlCla sludgecatalyst from the resin product without the formation of troublesomeemulsions by using high temperature, high pressure Washing methods.

The invention will he illustrated in greater detail by the followingexample and the accompanying diagram although it is not intended tolimit the invention specifically thereto.

Example 1 The selected steam cracked naphtha feed stream is pumped vialine 4 to the continuous reactor circulative system through 1ine6 to thewater cooler B and thence by line 7 to reactor A. An AlCl3 containingcatalyst consisting of AlCls complexed with washed polymerizate fromlines 16 and 3 enters the reactor system by means of line 2. Thepolymerization of the unsaturated naphtha feed takes place in thereactor system, mainly in reactor A, at a temperature of about 35 to 55C. The polymerization mixture of naphtha feed and catalyst slurry iscontinuously circulated by pumps via lines 5, 6 and 7 through watercooler B and reactor A. The holdup of the mixture in reactor A isequivalent to 0.6 to

6.0 v./v./hr. The circulation rate is in the range of 1/3 to 5 volumesof the reactor per minute. The polymerization reaction mixture iswithdrawn overhead from reactor A by line 8 to soaker C., After sufcienttime in the reactor circulating system A and soaker C, the reactorefliuent is pumped through an orifice mixer and to hydrolyzer D by line13. It is contacted with water introduced by line 14 and high pressuresteam by line 12 at a temperature of about 150 C. In the hydrolyzer D,the reaction mixture is separated from the water phase to removedissolved and entrained AlCls sludge and complexes from the hydrocarbonphase. A relatively high temperature is employed to minimize theemulsion and settling problems by hydrolyzing and dissolving as much aspossible of the complexed AlCla complexes in aqueous phase.

The aqueous phase is removed by line 15. The resin product is recoveredfrom the hydrocarbon phase. This hydrocarbon phase is passed by lines 16and 17 into low pressure flash drum E into which a small amount, 0.005to 0.5 weight percent, of ammonia is added to the system by lines 18 and19 to control corrosion. The bottoms from flash drum E are pumped bylines 2t) and 36 to a fired coil vaporizer furnace F. The efuent fromfurnace F is passed by line 35 to stripper column G which is operated atabout Z50-300 C. Steam is injected into the lower portion. Unpolymerizedhydrocarbons and low molecular weight polymers are taken overhead asstream 22 and combined with the flash drum overhead stream as a totalstream 21. The bottoms stream 34 from stripper 6 is removed as linishedresin pro-duct.

The combined vapor stream 21 is condensed and passed by line 23 tosettler l-I in which a hydrocarbon phase and an aqueous phase areobtained. The aqueous phase containing residual NHiCl and NHiOH isremoved by line 25. The hydrocarbon phase is passed by line 24 to acaustic treating stage I operating at about 150 C. After separating anaqueous phase the hydrocarbon solution is passed by line 26 todistillation tower I into which steam is injected. In tower I, unreactednaphtha is taken overhead by line 28 and condensed. A part is returnedto tower l by lines 30 and 31 as reflux, and the remainder removed asstream 29.

Low molecular weight polymer is removed as a bottoms stream from tower Jby line 32. If desired, a part may be passed by line 33 andcombined withstream 34 and thereby blended with the finished resin to controlsoftening point characteristics.

Example 2 A steam cracked distillate boiling in the range of 30 to llt-0C. and containing about 20% conjugated acyclic diolens, 53% olens and27% aromatics and less than 2 wt. percent cyclopentadiene monomers waspolymerized in a two-stage continuous process as described in Example l.The catalyst, comprising7 a complex or sludge of 25 Wt. percent AlCl3 inflash drum bottoms was fed to the system at a rate of l wt. percentAlCla on fresh feed. Fresh feed was added to the reactor at a rate of lv./v./hr. and the contents of the reactor were circulated at a rate of180 reactor volumes per hour. At an operating temperature of 45 C., theresin product in the effluent from first stage represented a 36 wt.percent yield of 90 C? softening point resin having a Gardner colorindex of 2L. The concentration of AlCls in the circulating reactorsolution was in the range of 4-6 Wt. percent. When the e'liiuent fromthe first stage was passed to a second stage having an additionalresidence time of one hour, the final yield of 90 C? softening pointresin was 37.9 wt. percent on the feed. When the rst reactorrecirculation rate was reduced to 20 reactor volumes per hour, the yieldof 90 C. softening point 1 Ring' and ball method ASTM E-28-51-JI. Colorot a solution of 1 gram of resin in 67 m1. of xylene.

resin dropped to 34 Wt. percent as compared to 36 Wt. percent yieldobtained at the higher circulation rate. In all `cases the productresins had ash contents lower than 0.04 Wt. percent.

The reactor etfluents from the above reactions were contacted with Water(0.5 volume/ volume resin solution) for 30 minutes at 150 C. The aqueouslayer separated clearly from the hydrocarbon phase and titration of theaqueous phase for HCl indicated over removal of AlCls from the resinsolution. The treated hydrocarbon solutions were then iiashed to recoverabout 20% of the unreacted hydrocarbons and then steam stripped to abottoms temperature of 260 C. to recover resin product. Water,hydrocarbons and ammonia or reaction products thereof were takenoverhead and condensed. Water was separated from the hydrocarbon layer.Further fractionation of the hydrocarbon layer gave 8-10 wt. percent ofliquid polymer and -92 wt. percent of a gasoline fraction.

Example 3 A sample of overhead hydrocarbon from the resin strippingoperation contained 0.037 wt. percent chlorine equivalent to about 0.14wt. percent alkyl chloride of an average Cr molecular weight. Thishydrocarbon was contacted with an excess of 4 wt. percent NaOH in anagitated pressure vessel at 150 C. Back titration of excess caustic inthe aqueous layer indicated that over of the alkyl chlorides had beenhydrolyzed.

Example 4 A series of polymerizations was carried out using a steamcracked distillate boiling in the range of 38 and C. The naphthacontained about 17% conjugated acyclic diolefins, 47% oleins and 36%aromatics and less than 2% cyclopentadiene monomers by weight. Thepolymerization system described in Example l was employed using a feedrate of 4 v./v./hr. and a circulation rate of reactor volumes per hour.The catalyst, comprising a complex or sludge of 30 wt. percent AlCls inWashed polymerizate, was added to the reactor circulating system at arate equivalent to about 0.75-1.0 wt. percent AlCls on fresh feed. Theeffluent from 'the first reaction stage was passed through a secondstage of the same size at the same rate. The resin yield represented 37wt. percent of 90 C. softening point resin based on the feed.

Example 5 Two stage polymerization was carried out with the naphtha ofExample 3 using solid AlCls to the extent of 0.25 wt. percent on freshfeed. The feed rate was-maintained at 1 v./v./hr. and the reactorcirculation rate was about 200 reactor volumes per hour. Residence timein in the second stage was one hour. In this case a 29.6 wt. percentyield of 95 C. softening point resin was obtained. The resin was lightcolored (Gardner color index of 2). When using the same reactionconditions except in that the percent AlCl3 on fresh feed was increasedto 2 wt. percent, a 36 wt. percent yield of 96 C. softening point resinwas obtained.

What is claimed is:

l. An improved process for making hydrocarbon resins which comprises thesteps of polymerizing a C5 plus unsaturated hydrocarbon stream boilingup to 280 C. with a fluid aluminum chloride catalyst, contacting inpresence of the remaining active catalyst the resulting reactant mixturewith water in liquid phase at about 10U-200 C. and subjecting thehydrolyzed mixture to stripping to recover an unreacted hydrocarbonfraction and a light-colored, low ash resin.

2. An improved process for making hydrocarbon resins which comprises thesteps of continuously polymerizing a diolefrn-containing Cs plusunsaturated hydrocarbon stream boiling from 20 to 280 C., in thepresence of an aluminum chloride catalyst complex, maintaining aneffective AlCls concentration within the reacting system of 2 to 10times that in the reactor effluent stream, hydrolyzing in presence ofthe remaining active catalyst the result fing reactant effluent withwater in the liquid phase at about 12S-175 C., separating from thehydrolyzed mixture an unreacted hydrocarbon fraction and alight-colored, low ash resin.

` 3. An improved process for making hydrocarbon resins which comprisesthe steps of continuously polymerizing a selected steam-crackedpetroleum fraction boiling from 2O to 280 C. and having unsaturatedcomponents by contact with a fluid aluminum chloride catalyst,subjecting the hydrocarbon phase fro-m the reactor to aqueous liquidphase hydrolysis in presence of the remaining active catalyst at atemperature of about 150 C., distilling un reacted petroleum naphthafrom the petroleum resin in the presence of ammonia, thereby obtaining alight-colored petroleum resin, having an ash content below 0.04 wt.percent.

4. An improved process for making resins from stea.l cracked hydrocarbonfractions which comprises the steps of continuously contacting anunsaturated fraction of C plus hydrocarbons boiling up to 280 C. with analuminum chloride complex in a reaction zone, maintaining the contactingconditions at 0.6 to 6.0 v./v./hr., subsequently hydrolyzing in presenceof the remaining active catalyst the hydrocarbon phase from the reactorin liquid phase at elevated pressure and temperature of about 150 C.,distilling the resulting mixture in the presence of ammonia, recovery ofan overhead gasoline fraction and a low ash, light-colored resin, andtreating the recovered gasoline fraction with caustic solution of 2 to10 wt. percent concentration at a temperature of about 150 C.

5. An improved process for making resins from steamcracked hydrocarbonfractions which comprises the steps of continuously polymerizing ahydrocarbon fraction having about -35 wt. percent diolefins, 40-70 wt.percent olens, 20-45 wt. percent aromatics and 0-20 wt. percentparaffins and naphthenes with a luid aluminum chloride complex catalystat a temperature of l0 to 60 C., maintaining an effective AlClaconcentration within the reactor of about 2 to 10 times that of thereactor effluent stream, subjecting the reactor effluent to a highpressure liquid phase hydrolysis in presence of the remaining activecatalyst at a temperature of about 150 C., and separating a solid,light-colored petroleum resin of low ash content from the hydrolyzedmixture.

6. An improved process-for making resins from steamcracked hydrocarbonfractions which comprises the steps of continuously polymerizing ahydrocarbon fraction having about 10-35 wt. percent diolens, 40-70 wt.percent olefins, 20-45 wt. percent aromatics and 0-20 wt. percentparafins and naphthenes with a fluid aluminum chloride complex catalystat a temperature of 10 to 60 C., maintaining an effective AlClgconcentration within the reactor of about 2 to 10 times that of thereactor effluent stream, subjecting the hydrocarbon phase of the reactoreffluent to a high pressure liquid phase hydrolysis in presence of theremaining active catalyst at a temperature of about C., and separating asolid, light-colored petroleum resin of low ash content from thehydrolyzed mixture.

7. An improved process for making hydrocarbon resin3 which comprises thesteps of continuously polymerizing with an AlCls-containing catalyst of0.25 to 3.0wt. percent concentration based on the fresh feed, in arecirculating reactor system having at least one reactor stage, astea1n-cracked distillate fraction boiling in the range of 30 to 140 C.and containing 10-35% acyclic conjugated dioletins,y 4070% o-lefins,20-45% aromatics and less than 2% cyclopentadiene monomers maintainingan effective AlClz concentration in the first stage of the recirculatingreactor system ofV 2 to 10 times that in the outlet stream from thereactor, maintaining a fresh feed stream rate of l to 4 v./v./hr. and acirculating rate of 20 to 300 reactor volumes per hour, subsequentlyhydrolyaing in presence of the remaining active catalyst the effluentfrom the reactor in the liquid phase at a temperature of about 150 C.,distilling unreacted petroleum naphtha from the petroleum resin, therebyobtaining a light-colored petroleum resin, having an ash content below0.04 wt. percent.

8. An improved process for making hydrocarbon resins which comprises thesteps of continuously polyrnerizing with an AlCla complex of 0.25 to 3.0wt. percent concentration based on the fresh feed, in a recirculatingreactor system having a multiplicity of reactor Stages, a steam crackeddistillate boiling in the range of 30 to 140 C. and having less than 2%cyclopentadiene monomers maintaining an effective AlCla concentration inthe lirststage of the recirculating reactor system of 2 to 10 times thatin the outlet stream from the reactor, maintaining a fresh feed streamrate of l to 4 v./v./hr. and a circulating rate of 20 to 300 reactorvolumes per hour, subsequently hydrolyzing in presence of the remainingactive catalyst the hydrocarbon phase from the reactor in liquid phaseat elevated pressure and temperature of about 150 C., distilling theresulting mixture in the presence of ammonia, to recover an overheadgasoline fraction and a low ash, light-colored resin, and treating therecovered gasoline fraction with caustic solution of 2 to 10 wt. percentconcentration at a temperature of about 150 C.

References Cited in the file of this patent UNITED STATES PATENTS1,982,708 Thomas Dec. 4, 1934 2,023,495 Thomas Dec. 10, 1935 2,039,363Thomas May 5, 1936 2,521,022 Rowland Sept. 5, 1950

1. AN IMPROVED PROCESS FOR MAKING HYDROCARBON RESINS WHICH COMPRISES THESTEPS OF POLYMERIZING A C5 PLUS UNSATURATED HYDROCARBON STREAM BOILINGUP TO 280* C. WITH A FLUID ALUMINUM CHLORIDE CATALYST, CONTACTING INPRESENCE OF THE REMAINING ACTIVE CATALYST THE RESULTING REACTANT MIXTUREWITH WATER IN LIQUID PHASE AT ABOUT 100-200* C. AND SUBJECTING THEHYDROLYZED MIXTURE TO STRIPPING TO RECOVER AN UNREACTED HYDROCARBONFRACTION AND A LIGHT-COLORED, LOW ASH RESIN.